Hydroxyether organosilicon compounds



United States Patent Ofitice 3,057,901 Patented Oct. 9, 1962 3,057,901 HYDROXYETHER ORGAN OSILICON COMPOUNDS Edwin P. Plueddemann, Midland, Mich, assignor to Dow Corning Corporation, Midland, Mich., a corporation of Michigan No Drawing. Filed May 13, 1960, Ser. No. 28,861 4 Claims. (Cl. 260-4481) This invention relates to organosilicon compounds containing the group OH -OHCHHO It is the object of this invention to provide novel compositions of matter which are useful as surfactants in the preparation of polyurethane foams and which are useful as emulsifying agents for organosiloxane fluids and as lubricants. Other objects and advantages will be apparent from the following description.

This invention relates to compositions of the formula in which R is selected from the group consisting of hydrogen, monovalent hydrocarbonoxy radicals, monovalent hydrocarbon radicals, monovalent halohydrocarbon radicals and monovalent halohydrocarbonoxy radicals, y has a value from to 3, R is a divflent radical attached to the silicon through a silicon-carbon bond and being selected from the group divalent hydrocarbon radicals, divalent halohydrocarbon radicals and divalent radicals composed of carbon, hydrogen and oxygen in the form of ether linkages, n has a value from 1 to 2, n being 1 when the C of the CH group is linked directly to R in a cycloaliphatic ring, R is an alkylene group of 2 to 4 inclusive carbon atoms, m is an integer of at least 1 and B is of the group hydrogen, monovalent hydrocarbon radicals, monovalent hydrocarbonoxy radicals and monovalent halohydrocarbon radicals.

The compositions of this invention can he monomeric silanes when all the R" groups attached to the Si are monovalent radicals such as hydrogen, hydrocarbon, hydrocarbonoxy, etc. In those cases in which two or less R groups are present, the compositions of this invention are dimeric 0r polymeric materials. These polymers can be either homopolymers or copolymers. In the latter case the copolymers can be those in which each silicon has a group group attached thereto or the copolymer can be one in which only some of the silicon atoms have such groups attached thereto.

This invention includes within its scope copolymers of from .001 to 99.999 mol percent siloxane units of the formula where R, y, R, a, n, R, m and B are as above defined and from .001 to 99.999 mol percent siloxane units of the formula AxSiO in which A is of the group hydrogen, monovalent hydrocarbon radicals, monovalent halohydrocarbon radicals, monovalent hydrocarbonoxy and halohydrocarbonoxy radicals and groups of the formula DSiA and DSiOSiA' in which D is a divalent hydrocarbon radical and A is the same groups as A and x has a value from 0 to 3 inelusive.

The compositions of this invention are best prepared by reacting an epoxide of the formula R' SIR OHCHn with alcohols of the formula H(OR') OB in the presence of a Lewis acid such as stannic chloride, AlCl BF etherate and FeCl at a temperature below C. Under these conditions there is a preferential reaction of the hydroxyl of the alcohol with the epoxy group. Under these conditions, there will be no appreciable reaction between the epoxy group and any secondary hydroxyls or silicon-bonded hydrogen groups in the system as long as any primary hydroxyl groups remain. The reaction is best carried out on a molar ratio of at least 1 mol of alcohol per mol of epoxy group in the organosilicon epoxide.

The organosilicon epoxides used as intermediates in this invention can be prepared by any of the methods described in applicants copending application Serial No. 747,579, filed July 10, 1958, the disclosure of which is hereby incorporated herein by reference.

Briefly two general methods are employed as shown in said application. One is the addition of an unsaturated epoxide such as allyl glycidyl ether or butadiene monoepoxide to a compound containing SiH groups in the presence of a platinum catalyst. This reaction goes at temperatures below 100 C.

The second general method is that of oxidizing an unsaturated hydrocarbon substituent on a silicon with peracetic acid. The latter method is particularly appropriate Where a is 0. For example,

. MBzSlCHfl O MegSiOHCHz This reaction is best carried out by gently warming 2. mixture of the organosilicon compound with the peracid.

The compositions of this invention which are siloxanes can be prepared either by hydrolyzing the corresponding silanes in which R is a hydrolyzable group or they can be prepared by first preparing polymeric siloxanes containing SiH groups and thereafter reacting these siloxanes with an unsaturated epoxide and then with the alcohol as above described.

For the purpose of this invention R" can be hydrogen or any monovalent hydrocarbonoxy radical such as methoxy, ethoxy, isopropoxy, octadecyloxy, ally-loxy, hexenyloxy, cyclohexyloxy, cyclopentyloxy, cyclohexenyloxy, phenoxy, tolyloxy, xenyloxy or propargyloxy; any monovalent hydrocarbon radical such as methyl, ethyl, butyl, isopropy'l, octadecyl, myricyl, vinyl, allyl, hexenyl, cyclohexyl, cyclopentyl, cyclohexenyl, phenyl, tolyl, xenyl, naphthyl, benzyl or beta-phenylethyl; any halogenated monovalent hydrocarbon radical such as chloromethy-l, bromobutyl, chlorovinyl, 3,3,3-trifluoropropyl, bromophenyl, bromotolyl, u,a,a-trifiuorotolyl, chlorocyclohexyl, iodocyclohexenyl, or chloroxenyl; and any halogenated hydrocarbonoxy radical such as chloromethoxy, betachloroethoxy, chlorophenoxy, bromoxenyloxy, chloromethallyloxy, perfluoroethoxy, or chlorocyclohexyloxy.

y can be 0 or any integer from 1 to 3. Thus, there can be from 0 to 3 R groups attached to the silicon atom.

In the compositions of this invention R is a divalent radical attached to the silicon through a silicon-carbon linkage. R can be any divalent hydrocarbon radical such as methylene, ethylene, butylene, phenylene, xenylene, tolylene or or any divalent halohydrocarbon radical such as chloroet-hylene, fluoroethylene, bromophenylene or bromoxenylene and any divalent ether radical of the type (-ROR) where R is as above defined and x is an integer of at least 1 such as radicals of the formula ,CH CH OCH CH Me -CH2CH2O CHCH:

and -CH OCH CH=CH-.

When a is 0, then the group CHOHCH is attached directly to the silicon atom. Also, when n is l, the group RoHoHoH comprises a cycloaliphatic ring such as, for example,

OH OH For the purpose of this invention R can be ethylene, propylene or butylene and these radicals can be either straight or branched chain. Thus, for example, R can be CH CH CH CH CH Mo OrHr --OHCH-.- or -OHCHr- In other words, the group R can be derived from a commercially available alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide.

As can be seen m can be any integer of at least 1. Preferably m has a value of from 1 to 2000. Thus, the compositions of this invention can be derived from either monoglycols or polyoxyalkylene glycols. It should be understood that it is not necessary that each R be the same. If desired, various combinations of the R radicals can be present in the same molecule.

B can be hydrogen or any monovalent hydrocarbon radical such as methyl, ethyl, butyl, octadecyl, allyl, hexenyl, isopropyl, phenyl, xenyl, tolyl, cyclohexyl, cyclol plication of Clyde L. Whipple entitled, A Method of Preparing Polyurethane Foams, filed May 13, 1960, Serial No. 28,857. The additional compositions of this invention are useful as emulsifying agents for siloxane fluids and for lubricants.

The following examples are illustrative only and should not be construed as limiting the invention which is properly delineated in the appended claims.

In the specification and claims the following abbreviations are employed: Me for methyl, Et for ethyl, Bu for butyl and Ph for phenyl.

Example I Octamethylcyclotetrasiloxane was equilibrated at room temperature with tetramethyldisiloxane in the presence of a catalytic amount of sulfuric acid for 20 hours. The acid was neutralized with sodium bicarbonate and the product obtained had the formula This siloxane was then reacted with a 50% molar excess of allyl glycidyl ether in the presence of 1 g. of a butanol solution of chloroplatinic acid containing 1% platinum. The mixture was stirred overnight and the product was then stripped to remove the excess allyl glycidyl ether. The liquid product obtained had the formula 200 g. of a butoxy endblocked monool consisting of a copolymer of ethylene oxide and propylene oxide in amount of 50% by weight of each and containing 80 total alkylene oxide units per molecule were mixed with 46 g. of the above epoxy siloxane, .5 g. of SnCL; catalyst and 250 cc. of benzene. The mixture was stirred overnight at C., then filtered and stripped to remove the solvent. The residue had a viscosity of 2062 cs. at 25 C. and a refractive index of 1.4544. This material had the formula 011 Me: Mcz Me: OH B110 (O2H40)4o( a 60)uGHzOEOHzO 93 0 (S 0)2oSi(CHz)aO CH2CHOH2(O CaHu)a4(O 2 04001311 hexenyl, benzyl or beta-phenylethyl, or any halo-hydrocarbon radical such as beta-chloroethyl, bromopropyl, chlorophenyl, perfluoroethyl, chlorocyclohexyl, chloroallyl, bromomethallyl and bromoxenyl. B can also be any halo-hydrocarbon radical such as beta-chloroethyl, chlorophenyl, bromoxenyl or perfiuoroethyl or any hydrocarbonoxy radical such as C H OPh, -CH(CH OEt) CH CH OMe and CH OMe.

As stated above, the siloxanes of this invention can be copolymerized with conventional siloxanes of the formula in which x can range from 0 to 3. These siloxane units can be of the formula SiOz, ASiO A SiO or A SiO For the purpose of this invention A can be any hydrocarbon radical such as methyl, ethyl, butyl, octadecyl, myricyl, vinyl, allyl, hexenyl, cyclohexyl, cyclohexenyl, cyclopentyl, phenyl, tolyl, xenyl, naphthyl, benzyl or beta-phenylethyl or any halogenated hydrocarbon radical such as chloromethyl, 3,3,3-trifluoropropyl, perfluorovinyl, chlorophenyl, bromoxenyl, and chloronaphthyl or A can be of the formula DSiA and DSiOSiA in which A is the same as A and D is a divalent hydrocarbon radical such as methylene, ethylene, propylene, phenylene, cyclohexylene, CH=CH, and

Gotham- Some of the products of this invention, particularly those in which the R" groups are methyl radicals, are particularly beneficial as surfactants in polyurethane foams as is described and claimed in the copending ap- Example 2 1 mol of tetraethylene glycol was mixed with .5 mol of 0 [(Hknorno (oam siiio and 1 g. of SnCl The mixture was allowed to stand overnight at 70 C. to give a fluid product having a viscosity of 506 cs. at 25 C., a specific gravity of 1.092 and a refractive index of 1.4608. The product had the formula OH M02 [H(O O2H4)4O CHzCHCHzO (0112):;81120 Example 3 181 g. of

600 g. of polyethylene glycol having a molecular weight of 600 and 2 g. of SnCl were mixed with stirring. The temperature rose to C. The reaction product was made alkaline with alcoholic KOH and then neutralized with C0 The product was stripped to C. at 100 mm. and filtered to give a fluid having a viscosity of 900 cs. at 25 C. The product had the formula Example 4 '1 mol of tetramethyldisiloxane was reacted with 1 mol of allyl glycidyl ether in accordance with the procedure of Example 1 to give the composition 0 Me: Me: HSiOS1(CHz)aO OHiOHBHi 3,057,901 This product was then mixed with 1 mol of vinylpenta- KOH and then the solution treated with CO to remove methyldisiloxane in the presence of 1 g. of the catalyst the excess KOH. The product was then filtered and of Example 1 and warmed to 150 C. The product was stripped to 100 C. at 100 mm. The resulting material was distilled at 120 to 140 C. at 1 mm. The resulting disa fluid having a viscosity of 300 cs. at 25 C. and had the tillate had a density of .930 and a refractive index of 5 formula 1.4346 both at 25 C. The formula was Example 7 10 Meg M62 Meg Following the procedure of Example 6, H(OC H 01-1 Masiosionzomsiosuonmo01320110112 Was reacted Wlth 423 g. of this siloxane were added to 750 g. of the 0 Me Me Me 0 monomethyl ether of polyethylene glycol having a mo- Q s OH2CHg Sl8OSi):OsiB2OH2 s lecular weight of 750 in the presence of 4 g. of SnCl 15 The mixture was warmed at 50 to 60 C. until all the in the proportion of 1 mol of the former to .5 mol of the epoxy groups had reacted. The product was a viscous latter to give the fluid composition of the formula H H 0 0 E(OO2HJ)IEO(: Mez Mez M82 S GHQOHZSi(OSi)KOSiOH2GH2 S O(C2H4O)13H fluid having the formula This materifl had a refractive index of 1.4703 at C.

Me2 MezMez OH and a specific gravity at 25 C. of 1.096. MesSiOSiOHzGHzSiOSi(CH2)aO OHQCHCHEO (O2H40)17MB Example 5 25 Example 8 The procedure of Example 4 was repeated except that when 1 mol of the Compound the glycol ether employed was 1500 g. of the monobutyl- 0 other of a copolymer of 50% by weigth ethylene oxide and 50% by weight propylene oxide which ether has a mo1eu1ar weight of 1500, Th lti d t h d h 1s reacted with 1 mol of ethylene glycol 1n the presence of formula stannic chloride at 50 C., the fluid composition M92 Me: ME: 0H M62 Me: OH MeaSiOSiCHzCHiSiO Si(OH2)s0CH2OHCH2O (G2H4O)11(Ca 10)1a HSiO Si(CH2) 3O CHzCHCHzO CHzCHzOH Example 6 is obtained. 1 mol of Exam le 9 Mei Mez Mei p OHiOHCHZ (01193 10 10)s 1( z)aO0Ha 2 When the following epoxy silicon compounds are reactwas reacted with 2 mols of polyethylene glycol having a ed on an equimolar basis with octapropylene glycol in molecular weight of 600 and 4 g. of SnC1 at room temthe presence of stannic chloride, the following products perature. The chloride was neutralized with alcoholic are obtained.

Epoxy Organosilieon Compound Product 0 Me Me 1 S CHzCHaSiO 5 HO (CaHaO)s CH CH SiO O MezMea OHl/IezMeg 2 OH2CHSiOSi HO (C3HaO)gCHzCHSiOSi. 3 Copolymer of mol percent vinylmethylsiloxane Oopolymer of 50 mol percent; vinylmethylsiloxane and 50 mol and 50 mol percent percent 3 0 Me Me S CHzCHqSiO HO(CaHeO)s S CHaCHzSiO.

O M9 OH Me 4 HgO-GH SiO HO(O3HO)$CHCH SiO.

0 E Ph OH Ph 5 0H2 HCH2O(CH2)a i(OEt)2 HO(CQHBO)BCHRCHCH20(CH2)3S1(0E17)1.

O g Meg] OH M63 1 6 HzCHCHzO (CHmSiO iSi H0(CaHa0)sCH2CHCHzO(CHz) SiO 81.

O i: Me: 0H M91] 7 CHzCHOHzO (01103810 laSiPh HO 3Ht0)sOH2CHCH2O (GHmSiO SiPh. 3 A copolymer 015 mol percent A copolymer of 5 mol percent Me OH Me CHQCHCHQO (CH1) 3SiO, the remainder of the HO (C3H60)8OHIOHOH2O (CHmSiO, the remainder of copolymer being monotrifluoropropylsiloxane. the copolymer being monotrifluoropropylsiloxane.

Epoxy Organosilicon Compound Product 9 A copolymer of 33% mol percent chlorophenyl- A copolymer of 33% mol percent chlorophenylmethylsiloxane,

lgethylsiloxane, 33% mol percent 33% mol percent 6 E Ph 011 Ph H: H CHiO (CH2 :S1O and 33% mol percent 110 (CiHeO)sCH2CHCH2O (OHzhSiO and 33% mol percent 0 Me 0H Me CH: HCHzO (CH2)3S1O H0 (CJHGO)8CH2OHCHIO (CH1) aSiO.

CQH4C] OH O H Cl 10 EIkHCHzCHzSKOEt): HO (OaHnO)aCH:CHCHzCHzSi%OlEt)z.

CHzCHzCFs 0H CH CH CF 11 c nzbnomomsuo 0511401), Ho canto)screencmouzsudouzitonl O (3/ w OH 12 H2 HCHClGHzSKCaHuh HO (CaHuO)sCHaCHCHClCHzSKCaHuh.

O g Me OH Me 13 H2 HCHrO(CzH40)s(CH2)sS1(0Ph)2 HO(C3HQO)5OH:CHCH:O(CzH4O)a(CH2)3sl(OPh)1.

OH; H OH OH H 14 HEHOCHCHzOCHnCHzSKOEt): HO(CaHoO)aOHnCHO CHEZH O CHflCHZSi(OEt Q.

P11, OH Ph 15 CHzCHCHaCHzSiOEt HO(CaHeO)5CH5CHCHzCHzSi6Et.

OH 16 HkHCHzCEhsiOan H0 (CaHoOhCHgCHCHzCHzSiOz/a.

Example 10 drocarbon radicals, divalent halohydrocarbon radicals when 1 mol of and divalent radicals composed of carbon, hydrogen and Et HO(CHCH2O CH(CH2OM9)1 is reacted with 1 mol of in the presence of stannic chloride, the siloxane of the formula When the following epoxy silicon compounds are reacted with the following glycols on a 1 to 1 molar basis in accordance with the method of Example 1, the following products are obtained:

oxygen in the form of an ether linkage, a has a value from 0 to 1 inclusive, n has a value from 1 to 2 inclusive, n being 1 when the C of the CH group is linked directly to R in a cycloaliphatic ring, R is an alkylene radical of from 2 to 4 inclusive carbon atoms, m is an integer of at least 4 and B is selected from the group consisting of hydrogen, monovalent hydrocarbon radicals, monovalent halohydrocarbon radicals and monovalent hydrocarbonoxy radicals.

2. A composition in accordance with claim 1 where R is methyl and y has a value from 1 to 2 inclusive.

3. As a composition of matter a copolymer of from .001 to 99.999 mol percent siloxane units of the formula in which y has a value from 0 to 2 inclusive, R" is selected from the group consisting of hydrogen, m0no- Epoxy silicon compound Glycol Product 0 MerMes MezMc: 0 EtOSiOSiCHaCHzCHCHz H(OC3H4)2000CH2OH=CH:-..-- EtOSiOSKCHrMOHOHQO(CzH4O)m0GH1OH=CH,.

O H Me: Me: M92 M83 0 CHr=CHSi SiCHzCHCH: ClCzH4O(CnH4O)5ooH CH:=CHSi SlOHzCHCHgO(C1H4O)5 C H4CI,

- O H MezMe: M82149: 0 Br OSlOSiCHaCHCH: PhO(CzH4)zoH Br OSIOSICH2CHCH2(OCgHOzoOPh.

That which is claimed is: 1. A composition of matter of the formula in which R is selected from the group consisting of hydrogen, monovalent hydrocarbonoxy radicals, mono- 70 valent hydrocarbon radicals, monovalent halohydrocarbon radicals, monovalent hydrocarbonoxy radicals and monovalent halohydrocarbonoxy radicals, R is a divalent radical attached to the silicon through a silicon-carbon linkage and being selected from the group consisting of divalent hydrocarbon radicals, divalent halohydrocarbon radicals and divalent radicals composed of carbon, hydrogen and oxygen in the form of an ether linkage, a has a value from 0 to 1 inclusive, n has a value from 1 to 2 inclusive, n being 1 when the C of the CH, group is linked directly to R in a cycloaliphatic ring, R is an alkylene radical of from 2 to 4 inclusive carbon atoms, m is an integer of at 7 least 4 and B is selected from the group consisting of hydrogen, monovalent hydrocarbon radicals, monovalent halohydrocarbon radicals and monovalent hydrocarbonoxy radicals and from .001 to 99.999 mol percent siloxane units of the formula axsio in which A is selected from the group consisting of hydrogen, monovalent hydrocarbon radicals, monovalent halohydrocarbon radicals, monovalent hydrocarbonoxy radicals and monovalent halohydrocarbonoxy radicals and radicals of the formula DSiA' and DSiOSiA' where D is a divalent hydrocarbon radical and A is the same as A and x has a value from 0 to 3 inclusive.

4. A copolymer in accordance with claim 3 in which R" is methyl, A is methyl, y has a value from 1 to 2 and x has a value from 2 to 3.

References Cited in the file of this patent FOREIGN PATENTS France Feb. 9, 1959 correctedbelow.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,057,901 October 9, 1962 Edwin P. Plueddemann It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as Column 2, lines 34 and35 the formula should appear as shown below instead of as in the patent:

Me SiCH=CH +O Me SiCHCH column 5, lines 10 and ll the formula should appear as shown below instead of as in the patent:

M82 Me2Me2 Me SiOSiCH CH SiOSi(CH OCH CHCH same column 5, lines 33 and 34, the formula should appear as shown belowinstead of as in the patent:

, 2 2 2 0a Me SiOSiCH CH SiOSi(CH OCH CHCH O(C H O) (C H O) Bu column 6 lines 6 and 7 the formula should appear as shown below instead of as in the patent:

0a 2 2- 2 on :olumns 5 and 6 in the table second column the second formula should appear as shown below instead of as in the )atent:

Me Me CH CHSiOSi Fame table, second column the seventh formula should appear is shown below instead of as in the patent:

CH CHCH O(CH SiO SiPh column 7, lines 34 to 36, the formula should aopear as shown below instead of as in the patent:

same column 7, lines 41 to 43, the formula should appear as shown below instead of as in the patent:

Et OH Me (MeOCH CHOCH CH) OCH CH(CH 310 Signed and sealed this 18th day of June 1963.

(SEAL) Attest:

ERNEST W, SWIDER DAVID L LADD Attesting Officer Commissioner of Patents 

1. A COMPOSITION OF MATTER OF THE FORMULA 